WO2005021507A1 - Derives d'azine, bactericides pour l'agriculture ou l'horticulture, et leur procede de production - Google Patents

Derives d'azine, bactericides pour l'agriculture ou l'horticulture, et leur procede de production Download PDF

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WO2005021507A1
WO2005021507A1 PCT/JP2004/012654 JP2004012654W WO2005021507A1 WO 2005021507 A1 WO2005021507 A1 WO 2005021507A1 JP 2004012654 W JP2004012654 W JP 2004012654W WO 2005021507 A1 WO2005021507 A1 WO 2005021507A1
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group
alkyl
general formula
alkyl group
substituted
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PCT/JP2004/012654
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English (en)
Japanese (ja)
Inventor
Tatsuya Masumizu
Hidehiro Tajino
Hiroyuki Okita
Masaru Watanabe
Hitoshi Wakabayashi
Motohiro Hiramatsu
Tomomi Tahara
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Hokko Chemical Industry Co., Ltd.
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Priority to JP2005513523A priority Critical patent/JP4456565B2/ja
Publication of WO2005021507A1 publication Critical patent/WO2005021507A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
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    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/28—Radicals substituted by nitrogen atoms
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    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/06—1,2,3-Thiadiazoles; Hydrogenated 1,2,3-thiadiazoles
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    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/70—Nitro radicals
    • C07D307/71—Nitro radicals attached in position 5
    • C07D307/72—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2
    • C07D307/74—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2 by hydrazino or hydrazono or such substituted radicals
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    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
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    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/42—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms with nitro or nitroso radicals directly attached to ring carbon atoms
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems

Definitions

  • the present invention relates to an azine derivative and a fungicide containing the same, particularly an agricultural / horticultural fungicide.
  • the compounds represented by the general formulas (VII) and (IX) have a certain bactericidal activity, and in particular, powdery mildews such as barley and cucumber, and wheat It has a high control effect against various plant diseases such as red rust.
  • these compounds have weak activity, especially against cucumber gray mold, and their control effect on plant diseases is not satisfactory.
  • An object of the present invention is to provide a novel azine derivative compound which stably exerts a high control effect at a lower concentration on plant diseases having the above-mentioned drawbacks, broader and broader spectrum plant diseases. And methods of their manufacture.
  • Another object of the present invention is to provide a fungicide using such a compound as an active ingredient, particularly a fungicide for agricultural and horticultural use.
  • the present inventors have conducted intensive studies to solve the above problems, and completed the present invention. As a result, they have found that an azine compound having a specific structure exhibits a preferable bactericidal activity, and that it is possible to effectively control diseases, especially plant diseases, by using a fibrous composition containing the azine compound as an active ingredient.
  • the present invention has been made based on powerful knowledge.
  • the present invention is as follows.
  • R 2 represents an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group or a haloalkyl group
  • R 2 represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group.
  • R 3 represents a hydrogen atom or an alkyl group;
  • R 4 represents a hydrogen atom or an alkyl group;
  • Hetero represents a hetero element ( ⁇ , S or ⁇ ).
  • Group, phenyl group (the phenyl group is substituted with a halogen atom or A 5- or 6-membered ring containing a heteroatom ( ⁇ or ⁇ ) (the 5- or 6-membered ring is substituted or unsubstituted with an alkyl group).
  • X represents a hydrogen atom, a halogen atom, an alkyl group or an anolexoxy group.
  • R in the general formula (I) is a hydrogen atom and is an R-methyl group.
  • An agricultural and horticultural fungicide comprising the azine derivative and / or a salt thereof according to any one of (1) to (5).
  • [In the formula, represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group or a haloalkyl group
  • R 2 represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group
  • R 3 represents a hydrogen atom or an alkyl group
  • R 4 represents a hydrogen atom or an alkyl group
  • Hetero represents a hetero element (0, S, or N).
  • Group, phenyl group (the phenyl group is substituted or unsubstituted by a halogen atom)
  • a 5- or 6-membered ring containing a telo atom (O or N) (the 5- or 6-membered ring is substituted or unsubstituted with an alkyl group).
  • X represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
  • R 2 represents an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxyalkynole group, an alkoxycarbonylalkyl group or a haloalkyl group
  • R 2 represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group
  • R 3 represents a hydrogen atom or an alkyl group
  • R 4 represents a hydrogen atom or an alkyl group
  • Hetero represents a hetero element (0, S, or N).
  • R represents an alkyl group and R represents a methyl group
  • a preferred compound has a bactericidal activity, and a fungicide for agricultural and horticultural use containing the same is an important disease of agricultural crops, which is an important disease of crops such as cucumber gray mold. It has a wide range of control effects against various diseases such as cucumber and barley powdery mildew and wheat rust. Furthermore, it has both preventive and therapeutic effects, and is useful as a fungicide for agricultural and horticultural use. Therefore, the present invention provides an excellent method for controlling plant diseases.
  • the azine derivative according to the present invention is a compound represented by the general formula (I).
  • the azine derivative of the present invention is preferably a compound represented by the general formula (II). That is, the group having an azine moiety is replaced with a group having a carbamic acid moiety (one CH N (R) COOR)
  • the compound is bonded to the 5-position carbon of the phenyl ring when the bonding position of 2 12 is 1-position. Further, among the compounds represented by the general formula ( ⁇ ), a compound in which X is bonded to the 2-position carbon of the phenyl ring is preferable.
  • R in the general formulas (I) and ( ⁇ ) is a force indicating an arbitrary group or atom, preferably hydrogen.
  • R is a hydrogen atom.
  • the alkyl group represented by R may be any alkyl group.
  • 11 is a C alkyl group. Specifically, methinole group, ethyl group 6
  • the alkenyl group represented by R may be any alkenyl group.
  • the alkynyl group represented by R is a force S that can be any alkynyl group, preferably a linear or alkynyl group.
  • the acid group represented by R may be any acyl group. Preferably, it is linear or branched.
  • an acetyl group, a propionyl group, Forces such as a bivaloyl group are not limited thereto.
  • the alkoxyalkyl group represented by R may be any alkoxyalkyl group.
  • the alkoxyalkyl group represented by R may be any alkoxyalkyl group.
  • the alkoxy moiety of the oxyalkyl group is preferably a straight-chain or branched C
  • methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, t-butoxy, n-pentyloxy, 2-methylbutoxy, 2,2-dimethylpropoxy, Powers include, but are not limited to, 3-methylbutoxy, n-hexyloxy, 2-methylpentyloxy, 3_ethylbutoxy, and the like.
  • alkyl moiety of the alkoxyanalkyl group examples include methylene, ethylene, 1-methylethylene, 2-methynoleethylene, n-propylene, n-butylene, 1_methylpropylene, 2_methylpropylene, 1,1-dimethylethylene, 2-dimethylethylene, 2,2-dimethylethylene, 1-methynolebutylene, 2-methylbutylene, 1,2-dimethylpropylene, 2-ethylpropylene, n-pentylene, 1-methylpentylene, 2,3- Forces include, but are not limited to, dimethylbutylene, 2-ethylbutylene, n-hexylene, and the like.
  • the alkoxycarbonylalkyl group represented by R is any alkoxycarbonylalkyl
  • the alkoxy moiety of the alkoxycarbonylalkyl group is preferably a straight-chain or branched C
  • alkyl moiety of the alkoxycarbonylalkyl group examples include methylene, ethylene, 1-methylenoleethylene, 2-methylenoleethylene, n-propylene, n-butylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylethylene , 1,2-dimethylethylene, 2,2-dimethylethylene, 1-methylbutylene, 2-methylbutylene, 1,2-dimethylpropylene, 2-ethylpropylene, n-pentylene, 1-methylpentylene, 2,3 -Forces including, but not limited to, dimethylbutylene, 2-ethylbutylene, n-hexylene and the like.
  • the haloalkyl group represented by R may be any haloalkyl group. Preferably, straight chain or
  • a branched C 1 -C haloalkyl group is a kill group.
  • a fluoromethyl group a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a pentafluoropropyl group, a pentafluorobutyl group, a pentafluoropentyl group, a pentafluorohexyl group, and the like.
  • the listed powers are not limited to these.
  • R in the above general formulas (I) and (II) represents any group or atom, but is preferably
  • R represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, a haloalkyl group or a cycloalkylalkyl group.
  • R is an alkyl group
  • the alkyl group represented by R is a force S that can be any alkyl group, preferably linear or branched.
  • a cyclized C—C alkyl group Specifically, a methinole group, an ethyl group, n-
  • the alkenyl group represented by R may be any alkenyl group.
  • the power S includes, but is not limited to, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-methyl-2-buturyl group, a 3-methyl-11-pentenyl group, and the like.
  • the alkynyl group represented by R may be any alkynyl group.
  • the alkoxyalkyl group represented by R may be any alkoxyalkyl group.
  • the alkoxyalkyl group represented by R may be any alkoxyalkyl group.
  • the alkoxy moiety of the oxyalkyl group is preferably a straight-chain or branched C-C
  • alkoxyalkyl group is preferably a straight-chain or branched C
  • C-Al 6 Kiren Specifically, methylene, ethylene, 1-methynoleethylene, 2-methynoleethylene, n-propylene, n-butylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylethylene, 1,2- Dimethylethylene, 2,2-dimethylethylene, 1-methylbutylene, 2-methylbutylene, 1,2-dimethylpropylene, 2_ethylpropylene, n-pentylene, 1-methylpentylene, 2,3-dimethylbutylene, Examples include, but are not limited to, 2-ethylbutylene, n-hexylene, and the like.
  • the haloalkyl group represented by R may be any haloalkyl group S, preferably linear
  • Pentafluoropentyl group pentafluorohexyl group and the like.
  • the cycloalkylalkyl group represented by R may be any cycloalkylalkyl group
  • the cycloalkyl moiety of the cycloalkylalkyl group is not particularly limited to a force such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • the alkyl moiety of the cycloalkylalkyl group is preferably a linear or branched C1-C6 anolexylene, specifically, methylene, ethylene, 1-methylenoleethylene, 2-methylethylene, n-propylene, n-butylene.
  • R in the above general formulas (I) and (II) represents any group or atom, but is preferably
  • the alkyl group is optional, but is preferably a linear, branched, or cyclized C 1 C alkyl group. Specifically, methyl group, Tinole, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, 3-methynobutyl, n —Hexyl group, 2-methylpentyl group, 3-ethylbutyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and the like, but are not limited thereto.
  • R in the above general formulas (I) and (II) represents any group or atom, but is preferably
  • the alkyl group is optional, but is preferably a linear, branched, or cyclized C 1 C alkyl group. Specifically, methyl group,
  • Tinole Tinole, n-propyl, i-propyl, n-butyl, s_butyl, i-butyl, t-butyl, n-pentyl, 2_methylbutyl, 2,2_dimethylpropyl , 3-methylbutyl, n-hexyl, 2-methylpentyl, 3-ethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like, but are not limited thereto. Of these, the most preferred R is a methyl group.
  • Hetero in the above general formulas (I) and (II) represents a ring containing a hetero element (preferably an oxygen atom ⁇ , a sulfur atom S or a nitrogen atom N), and the ring is a 5-membered ring or a 6-membered ring. It can be a ring or a fused ring. Specific examples include 5-membered rings such as imidazole, pyrazole, pyrrole, thiophene, furan, and isoxazole; 6-membered rings such as pyridine, pyrazine, and pyrimidine; and condensed rings such as indole, benzofuran, and furopyridine. But not limited to them. Hetero in the general formulas (I) and ( ⁇ ) means that these rings are bonded as a substituent.
  • Hetero includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom which may be substituted with an arbitrary halogen atom.
  • Hetero which may be substituted with an arbitrary alkyl group, is preferably a linear, branched, or cyclized C1-Calkyl group. Specifically, methyl
  • the alkyl moiety of the haloalkyl group, hydroxyalkyl group or alkoxyalkyl group which may be substituted with any haloalkyl group, hydroxyalkyl group or alkoxyalkyl group is a straight-chain or branched C1-C1 alkyl group.
  • C6 alkylene specifically, methylene, ethylene, 1-methinoleethylene, 2-methinoleethylene, n-propylene, n-butylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylethylene , 1,2-dimethylethylene, 2,2-dimethylethylene, 1-methylbutylene, 2-methylbutylene, 1,2-dimethylpropylene, 2_ethylpropylene, n-pentylene, 1-methylpentylene, 2,3- Forces include, but are not limited to, dimethylbutylene, 2-ethylbutylene, n-hexylene, and the like.
  • the halogen of the haloalkyl group can be any halogen atom.
  • the alkoxy of the alkoxyalkyl group is a linear or branched C1-C6 alkoxy, specifically, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, t- Butoxy, n-pentyloxy, 2-methylbutoxy, 2,2-dimethylpropoxy, 3-methylbutoxy, n-hexyloxy, 2-methylpentyloxy, 3-ethylbutoxy, and the like.
  • Hetero is preferably a straight-chain, branched or cyclized C 1 -C alkyl group which may be substituted with an arbitrary alkoxyalkyl group.
  • alkylcarbonyl Specifically, acetyl, propionyl, bivaloyl and the like can be mentioned.
  • the alkyl moiety of the acyloxyalkyl group is preferably C1-Calkyl. Specifically, methyl, ethyl, n-propyl, i-ep
  • Mouth pill n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, 2-methylbutyl
  • Hetero is the same as the acylone group which may be substituted with an arbitrary acyl group, and is the same as the above-mentioned acyl group of the acyloxyalkyl group, specifically, an acetyl group, a propionyl group And a bivaloyl group.
  • Hetero is a halogen atom which may be substituted with a phenyl group which may be substituted with any halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Elemental atoms and the like.
  • Hetero may be substituted by any alkyl group, or may be substituted by a 5- or 6-membered ring containing a hetero atom (O or N).
  • the 5-membered ring is preferably exemplified by pyrazole, 1,3-dioxolane and the like, and the 6-membered ring is preferably exemplified by pyrimidine and the like, but is not limited thereto.
  • the alkyl group as a substituent on the 5- or 6-membered ring containing a hetero atom () or N) substituted on Hetero is an arbitrary alkyl group, preferably a linear Or a branched or cyclized C—C alkyl group. Specifically, a methinole group, an ethyl group, n-
  • X in the above general formulas (I) and ( ⁇ ) is a force representing an arbitrary atom or group, preferably a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
  • the halogen atom represented by X may be any halogen atom, and specific examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the alkyl group represented by X may be any alkyl group. Preferably, it is a linear, branched, or cyclized C1-Calkyl group. Specifically, a methinole group, an ethyl group,
  • the alkoxy group represented by X may be any alkoxy group. Preferably, it is a linear or branched C-C alkoxy group. Specifically, methoxy group, ethoxy group, n-propo
  • the compounds represented by the general formulas (I) and (II) according to the present invention include their E / Z isomers.
  • the compounds represented by (I) and ( ⁇ ) according to the present invention include all of their possible EZZ isomers, and pure or substantially pure E or Z isomers, or EZZ isomer mixtures Including.
  • the compounds represented by the general formulas (I) and (II) according to the present invention include salts thereof.
  • Such salts can be easily conceived by those skilled in the art from the description of the present specification, and examples thereof include anionic salt and trimeric salt.
  • Hetero contains a nitrogen (N) atom, it can be an ammonium salt.
  • Such salts can be easily conceived by those skilled in the art from the description in the present specification, and examples thereof include hydrochloride.
  • Table 11 shows examples of the compound represented by the general formula (X) among the compounds represented by the general formula (I).
  • Table 12 shows examples of the compound represented by the general formula (XI) among the compounds represented by the general formula (I).
  • the compounds represented by the general formula (I) and the general formula ( ⁇ ⁇ ) according to the present invention can be synthesized by any method. Particularly preferred general production methods are shown below. In the following, a method for producing the compound represented by the general formula (I) will be described, but it goes without saying that the compound represented by the general formula (II) can be produced according to the production method.
  • the compound represented by the general formula (I) according to the invention is represented by the following reaction formula 1 or 2. Thus, they can be synthesized.
  • the compound represented by the general formula (V) is a compound known in the literature, and can be synthesized and used, for example, according to the method described in JP-A-2001-106666.
  • the compound represented by the general formula (III) can be synthesized by reacting the compound represented by the general formula (V) with hydrazine as a raw material. Such a synthesis method is known, and can be synthesized, for example, by the methods described in Reference Examples 1 and 2 in Examples of the present specification.
  • the compounds represented by the general formulas (IV) and (VI) can be synthesized by commercially available methods or known methods.For example, refer to Reference Example 3 in Examples of the present specification. It can be synthesized by the method described.
  • the reactions of Reaction Formula 1 and Reaction Formula 2 can be performed under any conditions, but are preferably performed in an inert organic solvent.
  • An inert organic solvent refers to an organic solvent that does not react with solutes, that is, raw materials, products, and the like (hereinafter, also referred to as “inert solvent”). More specifically, the compound represented by the general formula ( ⁇ ) or the general formula (V) is dissolved in an inert solvent, and the compound represented by the general formula (IV) or the general formula (VI) is added thereto. The reaction force can be obtained by adding.
  • the compound represented by the general formula (IV) or the general formula (VI) may be added as it is, but an inert solvent (a solvent which is the same as or different from the solvent in which the general formula (III) or the general formula (V) is dissolved) May be dissolved and added. Conversely, the compound represented by the general formula (III) or (V) is added to a solution of the compound represented by the general formula (IV) or (VI) and reacted. You can also.
  • the inert solvent includes all inert solvents that can be considered by those skilled in the art, and is preferably an aromatic hydrocarbon-based solvent including benzene, toluene, xylene, and chlorobenzene, and carbon tetrachloride.
  • Ethyl acetate diisopropyl ether, tetrahydrofuran, dioxane, etc.
  • nitrile solvents including acetonitrile, propionitrile, etc., ethyl acetate, ethyl ethyl propionate And the like, and an ester solvent including methanol, ethanol, n-propanol and the like.
  • the reactions of Reaction Formula 1 and Reaction Formula 2 can be carried out under any temperature conditions, but are preferably carried out at 0 to 120 ° C, more preferably at 20 to 80 ° C.
  • the reaction can be usually performed under normal pressure conditions, but can also be performed under reduced pressure conditions or pressurized conditions.
  • the reaction time of the reactions of Reaction Formula 1 and Reaction Formula 2 can be set to any time at which the reaction is completed.
  • the reaction is completed, for example, it can be confirmed that one or both of the raw materials in the solvent are consumed, for example, by TLC (thin layer chromatography). Generally, it is in the range of 1 hour to 24 hours.
  • an acid catalyst may be added to the reaction system.
  • the reaction rate can be increased by reducing the acid catalyst.
  • Preferred acid catalysts include p-toluenesulfonic acid monohydrate, camphorsulfonic acid, and the like. Those skilled in the art should be able to appropriately select an acid catalyst suitable for this reaction. It can be used in reactions.
  • reaction product After the completion of the reaction represented by Reaction Formula 1 and Reaction Formula 2, the reaction product is treated by a usual work-up technique, and is represented by the general formula (I), which is the target product, by a usual purification and isolation method. Can be obtained. Specifically, after completion of the reaction, water and an organic solvent such as benzene, toluene, chloroform, or ethyl acetate are added to perform extraction, whereby an organic solvent layer can be obtained.
  • organic solvent such as benzene, toluene, chloroform, or ethyl acetate
  • the obtained organic solvent layer is dried with a dehydrating agent such as anhydrous sodium sulfate and anhydrous magnesium sulfate, the solvent is distilled off, and if necessary, the target compound (I) is purified by chromatography and purification means such as Z or recrystallization. It is also possible to get a dehydrating agent such as anhydrous sodium sulfate and anhydrous magnesium sulfate.
  • R represents an alkyl group, an alkenyl group, an alkyninole group, an acyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group or a haloalkyl group
  • R 2 represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group.
  • R 3 represents a hydrogen atom or an alkyl group
  • R 4 represents a hydrogen atom or an alkyl group
  • Hetero includes a hetero element ( ⁇ , S or N)
  • a phenyl group (the phenyl group is substituted or unsubstituted with , And a 5- or 6-membered ring containing a heteroatom (O or N) (the 5- or 6-membered ring is substituted or unsubstituted with an alkyl group).
  • L may be replaced by one or more of the same or different groups and Z or an atom, and L is a hydrogen atom selected from a chlorine atom, a bromine atom, an iodine atom, a sulfonate group or a triflate group.
  • X represents a certain group or atom, and X represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
  • reaction of reaction formula 3 is carried out in an organic solvent, usually in the presence of 1.0 to 2.5 equivalents of a base, preferably 1 equivalent to the compound represented by the general formula (1-2).
  • the reaction can be carried out by reacting an equivalent amount of the reaction reagent RL.
  • L of the reaction reagent represents an arbitrary leaving group or atom, and is appropriately selected depending on the type of the reaction reagent, the type of the compound represented by (1-2) as the reaction substrate, the reaction conditions, and the like.
  • Examples of the leaving group or atom L include a halogen atom (such as iodine, bromine, chlorine, and fluorine atom), a sulfonyl group (such as a trifluoromethanesulfonyl group, a methanesulfonyl group, and a toluenesulfonyl group), and a carbonyl group (such as an acetyl group). ), But are not limited to these.
  • a halogen atom such as iodine, bromine, chlorine, and fluorine atom
  • a sulfonyl group such as a trifluoromethanesulfonyl group, a methanesulfonyl group, and a toluenesulfonyl group
  • a carbonyl group such as an acetyl group
  • the reaction of reaction formula 3 is preferably performed in an inert solvent.
  • the inert solvent includes any inert solvent that can be considered by those skilled in the art, but is preferably an aromatic hydrocarbon solvent including toluene, xylene, etc., a halogen solvent including chloroform, methylene chloride, and the like, and a dioxane.
  • examples include ether solvents such as sun, tetrahydrofuran, and getyl ether; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; and dimethyl sulfoxide.
  • reaction of reaction formula 3 can be carried out under any temperature conditions, preferably at 0 150 ° C, more preferably at 0 to 80 ° C. This reaction can also be carried out under reduced pressure or increased pressure, which can usually be carried out under normal pressure.
  • the reaction time of the reaction of Reaction Formula 3 can be any time at which the reaction is completed.
  • the reaction is completed, for example, one or both of the raw materials in the solvent are consumed.
  • the completion of the reaction can be confirmed, for example, by TLC (thin layer chromatography). Generally, it is in the range of 1 hour to 24 hours.
  • any base can be used, and it should be appropriately selected depending on the reaction conditions, for example, the type of the reaction reagent R_L and the type of the solvent.
  • Preferred bases include organic bases, including triethylamine, N, N-dimethylaniline, N, N-dimethylaminopyridine, potassium carbonate, sodium bicarbonate. And inorganic bases including sodium carbonate and sodium hydride.
  • the reaction product is treated by a usual work-up technique, and a target compound represented by the general formula (I) can be obtained by a usual purification and isolation method.
  • a target compound represented by the general formula (I) can be obtained by a usual purification and isolation method.
  • water and an organic solvent such as benzene, toluene, chloroform, or ethyl acetate are added to perform extraction to obtain an organic solvent layer.
  • the obtained organic solvent layer is dried with a dehydrating agent such as anhydrous sodium sulfate and anhydrous magnesium sulfate, the solvent is distilled off, and if necessary, the target compound (I) is purified by chromatography and / or recrystallization. ) Is also possible.
  • the compound represented by the general formula (I) may have a melting point, an infrared absorption spectrum,
  • the compound represented by the general formula (I) according to the present invention exhibits a bactericidal activity. Therefore, a composition containing the compound represented by the general formula (I) can be used as a fungicide. In particular, a composition containing the compound represented by the general formula (I) as an active ingredient can be used as an agricultural and horticultural fungicide.
  • a fungicide for agricultural and horticultural use containing the compound represented by the general formula (I) according to the present invention as an active ingredient
  • the composition of (hereinafter, also simply referred to as "the agricultural and horticultural fungicide of the present invention") is the same as that of a general agricultural and horticultural fungicide, except that the compound represented by the general formula (I) is contained as an active ingredient. be able to.
  • the normal composition is described in, for example, the Guide for Pesticide Formulations (edited by the Japanese Society of Pesticides Application Law, published by the Japan Plant Protection Association). That is, a compound represented by the general formula (I), a suitable carrier, an auxiliary agent, a surfactant, a binder, a stabilizer and the like (but not limited thereto) can be blended.
  • the fungicide composition for agricultural and horticultural use of the present invention can be formulated into any dosage form generally used as a dosage form of an agricultural chemical.
  • formulated into powders, coarse powders, DL (driftless) powders, flow dusts, fine granules, fine granules, granules, wettable powders, liquids, sols (flowables), emulsions and oils But not limited thereto.
  • the content of the compound represented by the general formula (I) in the agricultural and horticultural fungicide of the present invention can be appropriately selected depending on the dosage form of the preparation and the method of use. Generally preferred contents are in the range of 0.1-90% by weight, based on the total weight of the formulation.
  • the agricultural and horticultural fungicide of the present invention can be used in the same manner as the method in which a general agricultural and horticultural fungicide is used.
  • a general agricultural and horticultural fungicide in the case of wettable powders, liquids, emulsions, sols (flowables), wettable powders, or oils, dilute them 50 to 20-fold with water, and the active ingredient will generally have a concentration of 11 lOOOOppm.
  • the diluted solution can be applied to the foliage of the diseased site of the plant in the range of 50 to 300 litters per 10 ares of arable land, usually in the range of 100 to 200 l.
  • liquids, emulsions, or sols do not dilute with water or dilute it to within 50-fold, and as a micro-spray, the amount of 505,000 ml per 10 ares is mainly used.
  • Aerial spraying (including LV spraying, ULV spraying, S spraying, etc.) is also possible.
  • air Spraying is performed using a helicopter or the like.
  • N_ [2_chloro mouth—5_ (1_hydrazonoethyl) dissolved in ethanol (19.6 ml) was added.
  • Methyl [benzyl] carbamate 1.0 g, 3.91 mmol
  • 2_Acetyl-6_methylpyridin (1.06 g, 7.82 mmol) was added thereto, and the mixture was stirred for 10 hours while heating under reflux.
  • N_ [2-—black mouth—5_ (1_hydrazonoethyl) dissolved in toluene (5. Oml) was dissolved. ) Methyl benzyl] carbamate (0.2 g, 0.78 mmol) was added. To this, 2,4-dichloro-3-pyridinecarboxyaldehyde (0.14 g, 0.78 mmol) was added and stirred at room temperature for 4 hours.
  • N_ [2_chloro mouth—5_ (1_hydrazonoethyl) benzyl] carboxyl dissolved in ethanol (10.0 ml) Methyl bamate (0.40 g, 1.57 mmol) was added.
  • 5_ black mouth _2—chofencar Boxyanolaldehyde (0.50 g, 3.44 mmol) was freed from calo and stirred at room temperature for 1.5 hours.
  • N_ [3_ (l-hydrazonoethyl) benzyl] capillamine dissolved in toluene (43 Oml) was dissolved.
  • the acid methyl (3.8 g, 17.2 mmol) was obtained.
  • 2_acetinole_5-methinolefuran (4.3 g, 34.4 mmol) was stirred while heating under reflux for 14 hours.
  • N,:-dimethylformamide 5 ml was added, and sodium hydride (73 mg, 60%, oily, 1.83) was added. mmol), and cooled to 5 ° C. with ice cooling with stirring.
  • N- [3_ (l- ⁇ [1_ (5-methyl-2-furyl) ethylidene] hydrazono ⁇ ethyl) benzyl] methyl rubamate 0.3 g, 0.92 mmol
  • the mixture was cooled again to 5 ° C. by ice cooling, and methyl iodide (0.26 g, 1.83 mmol) was added dropwise to the mixture. After completion of the dropwise addition, the ice cooling was stopped, the temperature was returned to room temperature, and stirring was continued for 3.5 hours. After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate (50 ml), and the organic layer was separated. The obtained organic layer was washed twice with water, and then dried over anhydrous sodium sulfate.
  • N, N-dimethylformamide (5 ml) was added to a four-necked flask with a reflux condenser, a stirrer and a thermometer in a 30 ml container, and sodium hydride (73 mg, 60%, oily, 1.83 mmol) was added.
  • sodium hydride 73 mg, 60%, oily, 1.83 mmol
  • sodium hydride 73 mg, 60%, oily, 1.83 mmol
  • was added was cooled on ice with stirring and cooled to 5 ° C.
  • N- [3_ (l- ⁇ [1_ (5-methyl-2-furyl) ethylidene] hydrazono ⁇ ethyl) benzyl] methyl rubamate 0.3 g, 0.92 mmol
  • N_ [2_chloro mouth—5_ (1_hydrazonoethyl) benzyl] carboxyl dissolved in ethanol (10.Oml) Methyl bamate (0.50 g, 1.96 mmol) was added.
  • 2-acetinol 4-methylthiazole (0.28 g, 1.96 mmol)
  • chloroform 40 ml was collected and washed twice with a saturated aqueous sodium chloride solution. The organic layer was separated, and dried over anhydrous sodium sulfate.
  • N_ [2-methyl-4_ (1_hydrazonoethyl) benzyl] carbamine dissolved in toluene (26 ml) was added.
  • Methylate (3. Og, 12.8 mmol) was added.
  • 2_acetyl-5-methylfuran (2.5 g, 20.4 mmol) was stirred for 5 hours while heating under reflux.
  • N, N-dimethinolephonoremamide (10 ml) was carohydrate-free, and sodium hydrogen hydride (70 mg, 60% (1.76 mmol), and the mixture was cooled to 5 ° C. with ice cooling with stirring.
  • sodium hydrogen hydride 70 mg, 60% (1.76 mmol
  • methyl N_ [2-methyl-4- (1- ⁇ [1- (5-methylinole 2_furyl) ethylidene] hydrazono ⁇ ethyl) benzyl] benzylamine 0.5 g, 1.46 mmol).
  • reaction mixture was cooled to room temperature, ethyl acetate (50 ml) was added to the reaction mixture, and the mixture was washed twice with a saturated sodium chloride aqueous solution, and the organic layer was separated and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure to obtain 0.45 g (yield: 84%) of the title compound as a brown crystal (melting point measurement impossible (polymerization by heating)).
  • Powdering Example A mixture of the compound of Compound No. 34 (2 parts by weight), PAP (physical property improver) (1 part by weight) and clay (97 parts by weight) was uniformly pulverized and mixed to obtain an active substance. A powder containing 2% by weight of the component was obtained. In addition, each powder was obtained in the same manner except that the compounds described in Table 1 and Table 9 were used instead of the compound of Compound No. 34.
  • Examples of making wettable powder Compound No. 43 (20 parts by weight), potassium alkylbenzenesulfonate (3 parts by weight), polyoxyethylenenoerphenyl ether (5 parts by weight), and clay (72 parts by weight) Parts by weight) were uniformly mixed and pulverized to obtain a wettable powder containing 20% by weight of the active ingredient. Further, each wettable powder was obtained in the same manner except that each compound shown in Table 1 to Table 9 was used instead of the compound of Compound No. 43.
  • Example 14 [0140] Emulsification Example: Compound No. 77 (30 parts by weight), methylethyl ketone (40 parts by weight) and polyoxyethylene nonylphenyl ether (30 parts by weight) were mixed and dissolved. Thus, an emulsion containing 30% by weight of the active ingredient was obtained. Further, respective emulsions were obtained in the same manner except that the compounds shown in Table 1 and Table 9 were used instead of the compound of Compound No. 77.
  • Test Examples 14 to 14 are described for the usefulness of the azine derivative represented by the general formula (I) according to the present invention and the agricultural and horticultural fungicide containing the same as an active ingredient. See and clarify. However, the utility of the present invention is not limited to those demonstrated by these test examples.
  • the test compound number is the same as the compound number shown in Table 1 to Table 12.
  • Test Example 1 A test for controlling the effect of powdery mildew on wheat, a single-leaf seedling of barley (variety: Azuma Golden) cultivated in a plastic pot having a diameter of 6 cm in a greenhouse.
  • a diluent (100 ppm) of a wettable powder prepared in accordance with the method was sprayed (sprayed with foliage) at a rate of 10 ml per pot.
  • One day after the treatment with the drug oat powdery mildew was formed on another barley leaf in advance.
  • Conidia of bacteria (Erysiphe graminis) were inoculated on pots sprayed with the drug, and the disease was controlled in an artificial weather chamber at 20 ° C.
  • control value was calculated by the following formula 1.
  • the control value was converted to an evaluation value according to Table 13 below. This test was performed in triplicate with one pot per section per chemical concentration. The evaluation value of the average control effect was obtained.
  • Equation 1 Equation 1 ⁇ ⁇ ⁇
  • Comparative drug A uses the following comparative drug A and replaces the compound of the present invention.
  • Comparative drug A in Table 14 indicates the following compounds. Comparative drug A is described in WO 01/42201. This comparative drug A was also used as a comparative drug in Test Example 2 and Test Example 4.
  • control value was converted to an evaluation value according to Table 13 above. This test was performed in triplicate with one pot per section per chemical concentration. The evaluation value of the average control effect was obtained.
  • Test Example 3 Test for control effect of cucumber gray mold on 1.5-leaf stage seedlings of cucumbers (variety: Sagami Hanjiro) cultivated in a plastic pot having a diameter of 6 cm in a greenhouse according to Example 13.
  • the diluent (100 ppm) of the wettable powder prepared above was sprayed at 10 ml per pot (foliage spraying).
  • agar-containing agar pieces of Botrytis dnerea (Botrytis dinerea) cultured on a potato decoction medium were inoculated on the first leaf of the above-mentioned kiyuri at 20 ° C. Put in greenhouse.
  • the lesion diameter (cm) was measured.
  • the control value (%) was calculated by the above formula 3.
  • the control value was converted to an evaluation value according to Table 13 above. This test was performed in triplicate with one pot per section per chemical concentration. The average evaluation value of the control effect was obtained.
  • Control (%) [1 _ (spots in the spray area am / urn Diseases in the cloth area 3 ⁇ 4ra] ⁇ ⁇ ⁇ ⁇
  • a survey index (6-grade evaluation) of the degree of phytotoxicity to cucumber was investigated according to the above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pyridine Compounds (AREA)
  • Pyrrole Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Furan Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

L'invention porte sur de nouveaux composés dérivés d'azine de formule générale (I), stables et efficaces contre une gamme importante de maladies des plantes même à faible concentration, sur leur procédé de production, et sur des bactéricides spécialement à usage agricole et horticole, dont ces composés constituent le principe actif. Dans ladite formule: R1 représente hydrogène, alkyle, alcényle, alkynyle, acyle, alcoxyalkyle, alcoxycarbonylalkyle, ou haloalkyle; R2 représente alkyle, alcényle, alkynyle, alcoxyalkyle, haloalkyle, ou cycloalkylalkyle; R3 et R4 représentent chacun hydrogène ou alkyle; hétéro représente un cycle fusionné contenant des hétéroatomes; et X représente hydrogène, alkyle, ou alcoxy.
PCT/JP2004/012654 2003-09-01 2004-09-01 Derives d'azine, bactericides pour l'agriculture ou l'horticulture, et leur procede de production WO2005021507A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006056462A1 (fr) * 2004-11-26 2006-06-01 Basf Aktiengesellschaft Composes d'azine permettant de combattre les parasites des animaux
JP2009149598A (ja) * 2007-11-29 2009-07-09 Nippon Soda Co Ltd アジン誘導体および農園芸用殺菌剤
WO2010137302A1 (fr) * 2009-05-27 2010-12-02 日本曹達株式会社 Dérivés hétéroaryles contenant de l'azote et fongicides pour utilisation agricole et horticole
CN108977363A (zh) * 2018-07-19 2018-12-11 河南省农业科学院植物保护研究所 试验用小麦白粉病菌培养制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0499823A2 (fr) * 1991-02-20 1992-08-26 BASF Aktiengesellschaft Dérivés de phényle imino substitués, leur preparation et fongicides les contenant
EP0627411A1 (fr) * 1993-06-03 1994-12-07 BASF Aktiengesellschaft Dérivés azine de l'acide phénylacétique et fongicides les contenant
JP2000281648A (ja) * 1999-03-26 2000-10-10 Nippon Kayaku Co Ltd 殺虫性アジン誘導体
WO2001042201A1 (fr) * 1999-12-06 2001-06-14 Bayer Aktiengesellschaft N-phenylcarbamates a action microbicide, insecticide et acaricide
JP2004262821A (ja) * 2003-02-28 2004-09-24 Hokko Chem Ind Co Ltd アジン誘導体、その製造方法、および農園芸用殺菌剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0499823A2 (fr) * 1991-02-20 1992-08-26 BASF Aktiengesellschaft Dérivés de phényle imino substitués, leur preparation et fongicides les contenant
EP0627411A1 (fr) * 1993-06-03 1994-12-07 BASF Aktiengesellschaft Dérivés azine de l'acide phénylacétique et fongicides les contenant
JP2000281648A (ja) * 1999-03-26 2000-10-10 Nippon Kayaku Co Ltd 殺虫性アジン誘導体
WO2001042201A1 (fr) * 1999-12-06 2001-06-14 Bayer Aktiengesellschaft N-phenylcarbamates a action microbicide, insecticide et acaricide
JP2004262821A (ja) * 2003-02-28 2004-09-24 Hokko Chem Ind Co Ltd アジン誘導体、その製造方法、および農園芸用殺菌剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006056462A1 (fr) * 2004-11-26 2006-06-01 Basf Aktiengesellschaft Composes d'azine permettant de combattre les parasites des animaux
JP2009149598A (ja) * 2007-11-29 2009-07-09 Nippon Soda Co Ltd アジン誘導体および農園芸用殺菌剤
WO2010137302A1 (fr) * 2009-05-27 2010-12-02 日本曹達株式会社 Dérivés hétéroaryles contenant de l'azote et fongicides pour utilisation agricole et horticole
CN108977363A (zh) * 2018-07-19 2018-12-11 河南省农业科学院植物保护研究所 试验用小麦白粉病菌培养制备方法

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